Data compilation of ESOP

The work in this sub-project of ESOP focuses on the advective and convective transforma-tion of water masses in the Greenland Sea and its neighbouring areas. It includes observational work on the sub-mesoscale and analysis of hydrographic data up to the gyre-scale. Observations of active convective plumes were made with a towed chain equipped with up to 80 CTD sensors, giving a horizontal and vertical resolution of the hydrographic fields of a few metres. The observed scales of the penetrative convective plumes compare well with those given by theory. On the mesoscale the structure of homogeneous eddies formed as a result of deep convection was observed and the associated mixing and renewal of the intermediate layers quantified. The relative importance and efficiency of thermal and haline penetrative convection in relation to the surface boundary conditions (heat and salt fluxes and ice cover) and the ambient stratification are studied using the multi year time series of hydro-graphic data in the central Greenland Sea. The modification of the water column of the Greenland Sea gyre through advection from and mixing with water at its rim is assessed on longer time scales. The relative contributions are quantified using modern water mass analysis methods based on inverse techniques. Likewise the convective renewal and the spreading of the Arctic Intermediate Water from its formation area is quantified. The aim is to budget the heat and salt content of the water column, in particular of the low salinity surface layer, and to relate its seasonal and interannual variability to the lateral fluxes and the fluxes at the air-sea-ice interface. This will allow to estimate residence times for the different layers of the Greenland Sea gyre, a quantity important for the description of the Polar Ocean carbon cycle.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Age determination of sediment core HZM, lake Holzmar (Tables 1, 2)

AMS radiocarbon ages have been determined on terrestrial macrofossils selected from the annually laminated sediments of lake Holzmaar (Germany). The radiocarbon chronology of this lake covers the last 12.6 ka. Comparison of the radiocarbon dated varve chronology with tree ring data shows that an additional 878 years have to be added to the varve chronology. The corrected 14C varve chronology of Holzmaar reaches back to ca. 13.8 ka cal. BP and compares favourably with the results from Soppensee (Switzerland) (Hajdas et al., 1993, doi:10.1007/BF00209748). The corrected ages for the onset and the end of the Younger Dryas biozone are 11,940 cal. BP and 11,490 cal. BP, respectively. The ash layer of the Laacher See volcanic eruption is dated at 12,201 ± 224 cal. BP and the Ulmener Tephra layer is dated at 10,904 cal. BP.

(Table 1) Mean grain sizes and standard deviations of gas hydrate samples

Methane hydrates are present in marine seep systems and occur within the gas hydrate stability zone. Very little is known about their crystallite sizes and size distributions because they are notoriously difficult to measure. Crystal size distributions are usually considered as one of the key petrophysical parameters because they influence mechanical properties and possible compositional changes, which may occur with changing environmental conditions. Variations in grain size are relevant for gas substitution in natural hydrates by replacing CH4 with CO2 for the purpose of carbon dioxide sequestration. Here we show that crystallite sizes of gas hydrates from some locations in the Indian Ocean, Gulf of Mexico and Black Sea are in the range of 200-400 µm; larger values were obtained for deeper-buried samples from ODP Leg 204. The crystallite sizes show generally a log-normal distribution and appear to vary sometimes rapidly with location.

Geochemistry and sedimentation rates of ODP Leg 199 sites and of surface sediments in the eastern Pacific ocean

We present the first high-resolution organic carbon mass accumulation rate (MAR) data set for the Eocene equatorial Pacific upwelling region, from Sites 1218 and 1219 of the Ocean Drilling Program. A maximum Corg MAR anomaly appears at 41 Ma and corresponds to a high carbonate accumulation event (CAE). Independent evidence suggests that this event (CAE-3) was a time of rapid cooling. Throughout the Eocene, organic carbon burial fluxes were an order of magnitude lower than fluxes recorded for the Holocene. In contrast, the expected organic carbon flux, calculated from the biogenic barium concentrations for these sites, is roughly equal to modern. A sedimentation anomaly appears at 41 Ma, when both the measured and the expected organic carbon MAR increases by a factor of two-three relative to the background Eocene fluxes. The rain of estimated Corg and barium from the euphotic zone to the sediments increased by factors of three and six, respectively. We suggest that the discrepancy between the expected and measured Corg in the sediments is a direct consequence of the increased metabolic rates of all organisms throughout the Eocene oceans and sediments. This hypothesis is supported by recent work in ecology and biochemical kinetics that recognizes the fundamental basis of ecology as following from the laws of thermodynamics. This dependence is now elucidated as the Universal Temperature Dependence (UTD) "law" of metabolism and can be applied to all organisms over their biologically relevant temperature range. The general pattern of organic carbon and barium deposition throughout the Eocene is consistent with the UTD theory. In particular, the anomaly at 41 Ma (CAE-3) is associated with rapid cooling, an event that triggered slower metabolic rates for all organisms, slower recycling of organic carbon in the water and sediment column, and, consequently, higher deposition of organic carbon in the sediments. This "metabolism-based" scenario is consistent with the sedimentation patterns we observe for both Sites 1218 and 1219.

Radionuclides measured on water bottle samples

Actinium is one of the rarest naturally occurring elements on earth. We measured its longest-lived isotope 227Ac (half-life 21.77 yr) for the first time in the water column of the Southeast Pacific, the Central Arctic, the Antarctic Circumpolar Current (ACC) and the Weddell Gyre (WG). Besides the profile in the Southeast Pacific, which confirms earlier findings about the role of diapycnal mixing for 227Ac distribution, we found three other different types of vertical profiles. These profiles point to a prominent role of advection for 227Ac distribution, especially in the Southern Ocean. Depending on the type of profile found, 227Ac is proposed as a tracer for different oceanographic questions. In the Southern Ocean, up to 4.93±0.32 dpm/m**3 227Ac is found close to the sea floor, which is the highest concentration ever observed in the ocean. Close to the sea surface in the WG, 0.46±0.05 dpm/m**3 227Acex (227Ac in excess of its progenitor 231Pa) is detected. We use 227Acex there to determine the upwelling velocity in the Eastern WG to be about 55 m/yr. In the ACC, Upper and Lower Circumpolar Deep Water (UCDW and LCDW) are found to differ clearly in their 227Acex activity. High 227Acex activities are therefore a promising tracer for recent inputs of LCDW to the sea surface, which may help to understand the role of deep upwelling for iron inputs into Antarctic surface waters. The expected release of 227Ac is compared with 228Ra to make sure that the large near-surface excess in the water column of the Southern Ocean is not due to lateral inputs by isopycnal mixing. Data from the Central Arctic and from a transect across the ACC confirm that 228Ra and 227Acex differ strongly in their sources. The first measurements of 227Ac on suspended matter (less than 1.7% of total 227Ac close to the sea floor) indicate that the particle reactivity of 227Ac is negligible in the open ocean, in agreement with earlier findings [Y. Nozaki, Nature 310 (1984) 486-488]. Despite the extremely low concentrations of 227Ac, new measurement techniques [W.S. Moore, R. Arnold, J. Geophys. Res. 101 (1996) 1321-1329] point to a comfortable and comparably simple determination of 227Ac in the future. Finally, 227Acex may become a widely used deep-sea specific tracer.

Petrology, geochemistry and K-Ar Age determination of De Gerlache Seamount basalts

The De Gerlache Seamounts are two topographic highs in the Bellingshausen Sea, southeastern Pacific. Petrological and geochemical studies together with K-Ar age determinations were carried out on four dredged basalt samples collected during a RV Polarstern expedition (ANT-XII/4) in 1995. Minor and trace element composition suggest alkaline basalt compositions. Compared to alkaline basalts of adjacent West Antarctica (the Jones Mountains) and of Peter I Island, the samples have lower mg-numbers, lower Ni and Cr contents and lower high field-strength elements (HFSE)/Nb and large-ion lithophile elements (LILE)/HFSE ratios. Three of the four samples have low K, Rb, and Cs concentrations relative to alkaline basalts. The K-depletion and other elemental concentrations may be explained by 1.1% melting of amphibole bearing mantle material. Additionally, low Rb and Ba values suggest low concentrations of these elements in the mantle source. K-Ar age determinations yield Miocene ages (20-23 Ma) that are similar in age to other alkaline basalts of West Antarctica (Thurston Island, the Jones Mountains, Antarctic Peninsula) and the suggested timing of onset of Peter I Island volcanism (~10-20 Ma). The occurrence of the DGS and Peter I Island volcanism along an older but reactivated tectonic lineation suggests that the extrusions exploited a zone of pre-existing lithospheric weakness. The alkaline nature and age of the DGS basalts support the assumption of plume activity in the Bellingshausen Sea.

Seawater carbonate chemistry and accumulation of radiotracers in squid, Loligo vulgaris during experiments, 2011

The anthropogenic release of carbon dioxide (CO2) into the atmosphere leads to an increase in the CO2 partial pressure (pCO2) in the ocean, which may reach 950 ?atm by the end of the 21st century. The resulting hypercapnia (high pCO2) and decreasing pH ("ocean acidification") are expected to have appreciable effects on water-breathing organisms, especially on their early-life stages. For organisms like squid that lay their eggs in coastal areas where the embryo and then paralarva are also exposed to metal contamination, there is a need for information on how ocean acidification may influence trace element bioaccumulation during their development. In this study, we investigated the effects of enhanced levels of pCO2 (380, 850 and 1500 ?atm corresponding to pHT of 8.1, 7.85 and 7.60) on the accumulation of dissolved 110mAg, 109Cd, 57Co, 203Hg, 54Mn and 65Zn radiotracers in the whole egg strand and in the different compartments of the egg of Loligo vulgaris during the embryonic development and also in hatchlings during their first days of paralarval life. Retention properties of the eggshell for 110mAg, 203Hg and 65Zn were affected by the pCO2 treatments. In the embryo, increasing seawater pCO2 enhanced the uptake of both 110mAg and 65Zn while 203Hg showed a minimum concentration factor (CF) at the intermediate pCO2. 65Zn incorporation in statoliths also increased with increasing pCO2. Conversely, uptake of 109Cd and 54Mn in the embryo decreased as a function of increasing pCO2. Only the accumulation of 57Co in embryos was not affected by increasing pCO2. In paralarvae, the CF of 110mAg increased with increasing pCO2, whereas the 57Co CF was reduced at the highest pCO2 and 203Hg showed a maximal uptake rate at the intermediate pCO2. 54Mn and 65Zn accumulation in paralarvae were not significantly modified by hypercapnic conditions. Our results suggest a combined effect of pH on the adsorption and protective properties of the eggshell and of hypercapnia on the metabolism of embryo and paralarvae, both causing changes to the accumulation of metals in the tissues of L. vulgaris.

Geochemistry of microtektites from Victoria Land Transantarctic Mountains

We extended the petrographic and geochemical dataset for the recently discovered Transantarctic Mountain microtektites in order to check our previous claim that they are related to the Australasian strewn field. Based on color and composition, the 465 microtektites so far identified include two groups of transparent glass spheres less than ca. 800 µm in diameter: the most abundant pale-yellow, or normal, microtektites, and the rare pale-green, or high-Mg, microtektites. The major element composition of normal microtektites determined through electron microprobe analysis is characterized by high contents of silica (SiO2 = 71.5 ± 3.6 (1 sigma) wt%) and alumina (Al2O3 = 15.5 ± 2.2 (1 sigma) wt%), low total alkali element contents (0.50-1.85 wt%), and MgO abundances <6 wt%. The high-Mg microtektites have a distinctly higher MgO content >10 wt%. Transantarctic Mountain microtektites contain rare silica-rich (up to 93 wt% SiO2) glassy inclusions similar to those found in two Australasian microtektites analyzed here for comparison. These inclusions are interpreted as partially digested, lechatelierite-like inclusions typically found in tektites and microtektites. The major and trace element (by laser ablation - inductively coupled plasma - mass spectrometry) abundance pattern of the Transantarctic Mountain microtektites matches the average upper continental crust composition for most elements. Major deviations include a strong to moderate depletion in volatile elements including Pb, Zn, Na, K, Rb, Sr and Cs, as a likely result of severe volatile loss during the high temperature melting and vaporization of crustal target rocks. The normal and high-Mg Transantarctic Mountain microtektites have compositions similar to the most volatile-poor normal and high-Mg Australasian microtektites reported in the literature. Their very low H2O and B contents (by secondary ion mass spectrometry) of 85 ± 58 (1 sigma) ?g/g and 0.53 ± 0.21 ?g/g, respectively, evidence the extreme volatile loss characteristically observed in tektites. The Sr and Nd isotopic compositions of multigrain samples of Transantarctic Mountain microtektites are 87Sr/86Sr ~ 0.71629 and 143Nd/144Nd ~ 0.51209, and fall into the Australasian tektite compositional field. The Nd model age calculated with respect to the chondritic uniform reservoir (CHUR) is TNdCHUR ~ 1.1 Ga, indicating a Meso-Proterozoic crustal source rock, as was derived for Australasian tektites as well. Coupled with the Quaternary age from the literature, the extended dataset presented in this work strengthens our previous conclusion that Transantarctic Mountain microtektites represent a major southward extension of the Australasian tektite/microtektite strewn field. Furthermore, the significant depletion in volatile elements (i.e., Pb, B, Na, K, Zn, Rb, Sr and Cs) of both normal and high-Mg Transantarctic Mountain microtektites relative to the Australasian ones provide us with further confirmation of a possible relationship between high temperature-time regimes in the microtektite-forming process and ejection distance.

Sedimentology of cores from the shelf of Lazarev Sea, East Antarctica

Distinct facies types, classified in radiocarbon-dated sediments from the shelf of the Lazarev Sea, East Antarctica, reveal a detailed history of processes that have controlled sedimentation during the deglaciation over the last 10,000 yr. The ice retreat on this part of the Antarctic shelf started 9500 yr BP, marked by the deposition of laminated sediments, deposited from a floating ice shelf. These laminites, which occur on top of diamictons laid down from a grounded ice sheet, are the basal sediments of the postglacial sequence. The intensity of the Antarctic Coastal Current (ACC), directed by shelf morphology, controlled sedimentation of the postglacial facies. A residual glaciomarine sediment with the fine fraction winnowed by strong currents developed from 9000-8000 yr BP in the western part of the investigation area and from 9000-5000 yr BP in the eastern part, closer to the prominent 'Fenno Deep' trough. Current velocities apparently decreased between 8000 and 2000 yr BP due to a deflection of the ACC by advancing ice tongues to the east of the investigation area during the 'Hypsithermal'. This led to a deposition of fine-grained sediments, and clay mineralogy suggests a continental source, possibly near the grounding line of the Nivl Ice Shelf, rather than a winnowing of sediments near the shelf break or advection from deeper water. Current velocities intensified after 2000 yr BP, removed fine material from these sediments and led to a relict sediment, consisting of coarse bryozoan and molluscan debris.

Age and chemical composition of volcaniclastic rocks from the Sea of Japan

Petrographic and geochemical studies showed that Oligocene - Early Miocene volcaniclastic rocks from the southern part of the Sea of Japan are ascribed to high-potassium aluminous rocks of sub-alkaline volcanic series from active continental margins. A comparative analysis revealed spatiotemporal relation of Oligocene - Early Miocene subaerial volcanism of the Sea of Japan with Late Cretaceous and Eocene - Early Miocene ignimbrite volcanism of the East Eurasian margin. This allows to refer the volcaniclastic rocks of the Sea of Japan to the stage of ignimbrite volcanism that occurred during relative quiescence against general extension in the continental margin setting.

Physical, Geochemical, Geomechanical, Geophysical and Hydrodynamic Characterization and Anisotropy Assessment of Corvio Sandstone

Corvio sandstone is a ~20 m thick unit (Corvio Formation) that appears in the top section of the Frontada Formation (Campoó Group; Lower Cretaceous) located in Northern Spain in the southern margin of the Basque-Cantabrian Basin. Up to 228 plugs were cored from four 0.3 x 0.2 x 0.5 m blocks of Corvio sandstone, to perform a comprehensive characterization of the physical, mineralogical, geomechanical, geophysical and hydrodynamic properties of this geological formation, and the anisotropic assessment of the most relevant parameters. Here we present the first data set obtained on 53 plugs which covers (i) basic physical and chemical properties including density, porosity, specific surface area and elementary analysis (XRF - CHNS); (ii) the curves obtained during unconfined and confined strengths tests, the tensile strengths, the calculated static elastic moduli and the characteristic stress levels describing the brittle behaviour of the rock; (iii) P- and S-wave velocities (and dynamic elastic moduli) and their respective attenuation factors Qp and Qs, electrical resistivity for a wide range of confining stress; and (iv) permeability and transport tracer tests. Furthermore, the geophysical, permeability and transport tests were additionally performed along the three main orthogonal directions of the original blocks, in order to complete a preliminary anisotropic assessment of the Corvio sandstone.

Chemical composition of Late Cenozoic volcanic and volcaniclastic deposits from the western Woodlark Basin area, SW Pacific

Tephra fallout layers and volcaniclastic deposits, derived from volcanic sources around and on the Papuan Peninsula, form a substantial part of the Woodlark Basin marine sedimentary succession. Sampling by the Ocean Drilling Program Leg 180 in the western Woodlark Basin provides the opportunity to document the distribution of the volcanically-derived components as well as to evaluate their chronology, chemistry, and isotope compositions in order to gain information on the volcanic sources and original magmatic systems. Glass shards selected from 57 volcanogenic layers within the sampled Pliocene-Pleistocene sedimentary sequence show predominantly rhyolitic compositions, with subordinate basaltic andesites, basaltic trachy-andesites, andesites, trachy-andesites, dacites, and phonolites. It was possible to correlate only a few of the volcanogenic layers between sites using geochemical and age information apparently because of the formation of strongly compartmentalised sedimentary realms on this actively rifting margin. In many cases it was possible to correlate Leg 180 volcanic components with their eruption source areas based on chemical and isotope compositions. Likely sources for a considerable number of the volcanogenic deposits are Moresby and Dawson Strait volcanoes (D'Entrecasteaux Islands region) for high-K calc-alkaline glasses. The Dawson Strait volcanoes appear to represent the source for five peralkaline tephra layers. One basaltic andesitic volcaniclastic layer shows affinities to basaltic andesites from the Woodlark spreading tip and Cheshire Seamount. For other layers, a clear identification of the sources proved impossible, although their isotope and chemical signatures suggest similarities to south-west Pacific subduction volcanism, e.g. New Britain and Tonga- Kermadec island arcs. Volcanic islands in the Trobriand Arc (for example, Woodlark Island Amphlett Islands and/or Egum Atoll) are probable sources for several volcaniclastic layers with ages between 1.5 to 3 Ma. The Lusancay Islands can be excluded as a source for the volcanogenic layers found during Leg 180. Generally, the volcanogenic layers indicate much calc-alkaline rhyolitic volcanism in eastern Papua since 3.8 Ma. Starting at 135 ka, however, peralkaline tephra layers appear. This geochemical change in source characteristics might reflect the onset of a change in geotectonic regime, from crustal subduction to spreading, affecting the D'Entrecasteaux Islands region. Initial 143Nd/144Nd ratios as low as 0.5121 and 0.5127 for two of the tephra layers are interpreted as indicating that D'Entrecasteaux Islands volcanism younger than 2.9 Ma occasionally interacted with the Late Archean basement, possibly reflecting the mobilisation of the deep continental crust during active rift propagation.

Distribution of planktic foraminifera in surface sediments of the Atlantic Ocean

We present a data set of 738 planktonic foraminiferal species counts from sediment surface samples of the eastern North Atlantic and the South Atlantic between 87°N and 40°S, 35°E and 60°W including published Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) data. These species counts are linked to Levitus's [1982] modern water temperature data for the four caloric seasons, four depth ranges (0, 30, 50, and 75 m), and the combined means of those depth ranges. The relation between planktonic foraminiferal assemblages and sea surface temperature (SST) data is estimated using the newly developed SIMMAX technique, which is an acronym for a modern analog technique (MAT) with a similarity index, based on (1) the scalar product of the normalized faunal percentages and (2) a weighting procedure of the modern analog's SSTs according to the inverse geographical distances of the most similar samples. Compared to the classical CLIMAP transfer technique and conventional MAT techniques, SIMMAX provides a more confident reconstruction of paleo-SSTs (correlation coefficient is 0.994 for the caloric winter and 0.993 for caloric summer). The standard deviation of the residuals is 0.90°C for caloric winter and 0.96°C for caloric summer at 0-m water depth. The SST estimates reach optimum stability (standard deviation of the residuals is 0.88°C) at the average 0- to 75-m water depth. Our extensive database provides SST estimates over a range of -1.4 to 27.2°C for caloric winter and 0.4 to 28.6°C for caloric summer, allowing SST estimates which are especially valuable for the high-latitude Atlantic during glacial times.